CN114656399A - Cavity spirochete imine silver complex - Google Patents
Cavity spirochete imine silver complex Download PDFInfo
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- CN114656399A CN114656399A CN202210254596.2A CN202210254596A CN114656399A CN 114656399 A CN114656399 A CN 114656399A CN 202210254596 A CN202210254596 A CN 202210254596A CN 114656399 A CN114656399 A CN 114656399A
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/53—Nitrogen atoms
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Abstract
A spirochete imine silver complex (I) having the formula:
Description
One, the technical field
The invention relates to an organic metal supermolecule coordination compound and a preparation method thereof, in particular to an organic metal supermolecule coordination compound with a cage-shaped structure and a preparation method thereof, and specifically relates to a cavity spirochete imine silver complex and a synthesis method thereof.
Second, background Art
In recent decades, cage-like organometallic supramolecular complexes have been rapidly developed, and Jonathan r.
At present, the ligand molecule design of the cage-shaped organic metal supermolecule coordination compound (hereinafter referred to as cage-shaped complex) is more and more biased to select the organic macromolecule with high structural symmetry, so as to construct the coordination compound with larger internal cavity volumeA compound (I) is provided. The preparation of the cage-shaped complex can be achieved by a self-assembly method of highly symmetrical organic ligand molecules and specific metal salts, and the reaction yield is high and the reproducibility is strong. The cage-shaped complex molecules have certain space inside, can be well combined with the guest molecules, and further influence the chemical environment of the host and the guest molecules to cause1Change in H NMR shift.
In recent years, cage complexes have played a prominent role in many fields. In the field of molecular recognition, the size, shape, selectivity and dynamic self-assembly of the metal-organic cage complex enable the metal-organic cage complex to selectively perform signal response after being bonded with guest molecules, and signals are easy to detect and collect due to the fact that the guest bonding behavior is amplified during molecular recognition. Frank Turthner topic group utilizes perylene imide (PBI), triamine derivatives and zinc salt to synthesize an example of M with strong fluorescence property by a coordination-driven self-assembly strategy4L6Tetrahedral metal-organic cage complexes. The cage-shaped complex generates obvious fluorescence quenching after a plurality of electron-rich pyrene and other guest molecules are included, so that the cage-shaped complex has important application value in host-guest fluorescence recognition. In the field of printing and dyeing industry, schelike chemists and other scientists introduce a cage-shaped compound capable of capturing anionic dye molecules into a polymer composite material with a fluorocarbon chain segment to form a stable complex, so that the material can be used for anti-staining treatment of fabrics, and the application of the cage-shaped compound in the aspect of textile printing and dyeing is pioneered. In the field of catalysis, professor M.FuJita first proposes a concept of 'molecular reactor', and utilizes a precisely designed cavity structure of a cage-shaped complex to apply a water-soluble supramolecular cage to Diels-Alder reaction. The cavity of the cage-shaped compound can contain diene and dienophile at the same time, but the limitation of the cavity enables the final product to be a 1, 4-position addition product. The product can not be realized by adopting the traditional catalytic reaction, and shows the unique catalytic stereoselectivity of the metal-organic supermolecule complex. In the field of pharmacy, the surface of a metal-organic polyhedral cage-shaped complex constructed by scientists such as Soumen K.Samanta and the like has 24 methyl viologen groups and is combined with cucurbituril [8 ]]Followed by charge transfer via heteroatom intercalation with the precursor of the antimycotic drugTo synthesize MOP-7. MOP-7 improves bioavailability (easy to be absorbed by cells) on the basis of keeping the physiological activity of drug molecules. In addition, MOP-7 and related structures thereof can benefit from longer in vivo circulation time to reduce side effects caused by preferential accumulation of EPR effect in tumors, and play a great role in improving the quality of life of patients.
In the future, by utilizing the characteristics of the host-guest relationship of the cage-shaped complex, the cage-shaped complex provides a good way for the creation research and application of functional materials.
Disclosure of Invention
The invention aims to provide a spirochete imine silver complex.
Another object of the present invention is to provide a process for the preparation of the above complexes.
The technical scheme of the invention comprises the following steps:
a spirochete imine silver complex has a structure shown as a general formula (I):
a process for preparing a borrelia imine silver complex according to claim 1. 2, 7-di (4-nitrophenoxy) naphthalene is prepared by taking 2, 7-naphthalenediol and p-chloronitrobenzene as raw materials, and 4, 4' - (naphthalene-2, 7-diyl dioxy) diphenylamine is obtained by iron powder reduction; pyridine-2-formaldehyde, 4' - (naphthalene-2, 7-diyl dioxy) diphenylamine and silver trifluoromethanesulfonate are used to synthesize the complex (I) through self-assembly. The reaction process is as follows:
the conditions in reaction (3) were: the reaction solvent can be selected from acetonitrile, methanol and pyridine, and acetonitrile is preferred; the reaction temperature can be selected from 30-70 ℃, preferably 48-52 ℃. The invention adopts a self-assembly synthesis method, directly obtains the target complex by one-step reaction, and has high reaction yield and strong reproducibility.
The complex (I) and guest compounds have unique subject-guest chemical relationship, so that the complex has wide application potential as a functional material.
Drawings
FIG. 1 is a nuclear magnetic stacking diagram of a host-guest relationship between a complex (I) and sodium tetraphenylboron. The figure shows that: after the sodium tetraphenylboron serving as a guest representative is added into the host complex (I), a strong host-guest binding effect is shown.
Detailed Description
Example 1
This example illustrates the preparation of 4, 4' - (naphthalene-2, 7-diylbiphenoxy) diphenylamine
1.6g (10mmol) of 2, 7-naphthalenediol, 3g (22mmol) of anhydrous potassium carbonate, 20mL of DMF and 5mL of toluene were sequentially introduced into a 50mL three-necked flask. After stirring, heating and reflux reaction, 3.5g (22mmol) of p-chloronitrobenzene is added for continuous reflux reaction for 8 hours. After the reaction is finished, cooling to 70 ℃, and performing suction filtration, cooling the filtrate, standing, performing suction filtration, washing and drying to obtain 2.01g of 2, 7-bis (4-nitrophenoxy) naphthalene, wherein the yield is as follows: 47%, melting point: 178 ℃ and 181 ℃.1H NMR(400MHz，CD3CN)：8.26(d，J＝2.4Hz，1H，benzene-H)，7.97(d，J＝8.8Hz，1H，benzene-H)，7.45(d，J＝2.3Hz，1H，benzene-H)，7.28(d，J＝2.3Hz，1H，benzene-H)，7.12(d，J＝2.4Hz，1H，benzene-H)。
A50 mL flask was charged with 0.402g (1.0mmol) of 2, 7-bis (4-nitrophenoxy) naphthalene, 0.82g (15mmol) of ammonium chloride, 15mL of ethanol and 5mL of water in this order, and the mixture was stirred and heated to 80 ℃. Adding 0.81g (15mmol) of 100-mesh high-activity reduced iron powder for three times, refluxing for 5 hours, filtering while hot, washing a filter cake with hot ethanol, adjusting the pH of the obtained filtrate to about 9 with sodium bicarbonate, filtering, desolventizing, drying the obtained crude product, dissolving the crude product with 0.5mol/L hydrochloric acid, filtering, adding 5% sodium hydroxide solution into the filtrate to adjust the pH to about 7, filtering, washing with water to obtain 0.157g of offwhite 4, 4' - (naphthalene-2, 7-diyldioxy) diphenylamine, wherein the yield is 43 percent, and the melting point is as follows: 167 ℃ and 168 ℃.1H NMR(400MHz，CD3CN): 7.81(d, J ═ 8.9Hz, 1H, benzene-H), 7.06(d, J ═ 8.6Hz, 1H, benzene-H), 6.94(s, 1H, benzene-H), 6.79(d, J ═ 8.6Hz, 1H, benzene-H), 6.60(d, J ═ 8.2Hz, 1H, benzene-H), 4.99(s, 2H, amino-H). IR (KBr pellets), cm-1：3415，1632，1498，1227，1156，839。
Example 2
This example illustrates the preparation of borrelia imine silver complexes and the study of host-guest properties
(1) Preparation of Complex (I)
In a 25mL flask were added 19.08mg (0.057mmol) of 4, 4' - (naphthalene-2, 7-diylbenzoxy) diphenylamine, 14.33mg (0.057mmol) of silver trifluoromethanesulfonate, 12mg (0.112mmol) of pyridine-2-carbaldehyde and 3mL of acetonitrile in this order, and reacted at 50 ℃ for 24 hours. After the reaction is finished, 10mL of isopropyl ether is added to separate out a solid, a yellow solid is obtained after centrifugal separation, and the isopropyl ether is washed and dried to obtain a product of 13 mg. The yield was 48%, the melting point > 300 ℃.1H NMR(400MHz，CD3CN)：8.82(s，1H，imine-H)，8.71(s，1H，pyridine-H)，8.11(td，J＝7.7，1.8Hz，1H，pyridine-H)，7.92(d，J＝7.5Hz，1H，pyridine-H)，7.77(d，J＝9.1Hz，1H，benzene-H)，7.67(dd，J＝5.6，1.8Hz，1H，pyridine-H)，7.37(d，J＝8.1Hz，1H，benzene-H)，7.06(dd，J＝8.9，2.1Hz，1H，benzene-H)，6.97(s，1H，benzene-H)，6.91(d，J＝8.3Hz，1H，benzene-H)。ESI-MS m/z：629.09[Ag2L2]2+，1405.13[Ag2L2]2+[OTf]-。
(2) Study of host and guest Properties
Complex (I) and NaBPh4Has better solubility in acetonitrile, and aims to maintain the complex (I) + NaBPh4The total concentration is unchanged, and the complex (I) and NaBPh4Were all prepared as 0.01mmol/ml solutions. 77.75mg of complex (I) was weighed and dissolved in deuterated acetonitrile to a solution volume of 5 mL. Weighing 17.1mg NaBPh4And dissolving the mixture with deuterated acetonitrile to the volume of 5mL of the solution. And (4) transferring the corresponding volume of the subject and object solution to a glass tube by using a liquid transfer gun according to the relevant proportion, reacting at room temperature for 2 hours, and directly using the reaction solution for nuclear magnetic testing.
Complex (I) with NaBPh4The nuclear magnetic stacking diagram of the subject-object relationship is shown in the attached figure 1. As can be seen, the complex (I) reacts with NaBPh4Has good host-guest effect, so that the functional material has wide application potential.
Claims (3)
1. A spirochete imine silver complex has a structure shown as a general formula (I):
2. a process for preparing the cavitrotospiroimine silver complex of claim 1, synthesized from pyridine-2-carbaldehyde, 4' - (naphthalene-2, 7-diylbutoxy) diphenylamine and silver triflate by self-assembly. The reaction process is as follows:
3. the method of claim 2, wherein: the reaction solvent in the reaction (1) is selected from acetonitrile, methanol and pyridine, preferably acetonitrile; the reaction temperature is 30-70 ℃, preferably 48-52 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108912096A (en) * | 2018-06-22 | 2018-11-30 | 南京工业大学 | A kind of leptospira structure imines iron complex |
| CN109438420A (en) * | 2018-11-08 | 2019-03-08 | 南京工业大学 | A kind of imines zinc s-triazine complex |
| CN110041308A (en) * | 2018-01-16 | 2019-07-23 | 南京工业大学 | A kind of high symmetry sandwich structure imines Zn complex |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041308A (en) * | 2018-01-16 | 2019-07-23 | 南京工业大学 | A kind of high symmetry sandwich structure imines Zn complex |
| CN108912096A (en) * | 2018-06-22 | 2018-11-30 | 南京工业大学 | A kind of leptospira structure imines iron complex |
| CN109438420A (en) * | 2018-11-08 | 2019-03-08 | 南京工业大学 | A kind of imines zinc s-triazine complex |
Non-Patent Citations (2)
| Title |
|---|
| JEONG JUN LEE等: "Coordination-cyclodimeric array containing both channels and cages: photoluminescence recognition of diiodomethane", 《CRYSTENGCOMM》, vol. 19, no. 23, pages 3117 - 3123 * |
| WEN-YUAN WU等: "Self-assembly and peripheral guest-binding of [Zn3L2(H2O)6]6+ triangular double helicate", 《INORGANIC CHEMISTRY COMMUNICATIONS》, vol. 89, pages 1 - 4 * |
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